CN102701315A - Method for processing dye wastewater by applying nanocomposite photocatalyst combination-Fenton - Google Patents

Method for processing dye wastewater by applying nanocomposite photocatalyst combination-Fenton Download PDF

Info

Publication number
CN102701315A
CN102701315A CN2012102186538A CN201210218653A CN102701315A CN 102701315 A CN102701315 A CN 102701315A CN 2012102186538 A CN2012102186538 A CN 2012102186538A CN 201210218653 A CN201210218653 A CN 201210218653A CN 102701315 A CN102701315 A CN 102701315A
Authority
CN
China
Prior art keywords
tio
waste water
fenton
dye wastewater
base
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN2012102186538A
Other languages
Chinese (zh)
Other versions
CN102701315B (en
Inventor
孙岚
苏钰丰
吴奇
林昌健
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Guangdong Huafeng Bijiang Environmental Technology Co. Ltd.
Original Assignee
Xiamen University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen University filed Critical Xiamen University
Priority to CN201210218653.8A priority Critical patent/CN102701315B/en
Publication of CN102701315A publication Critical patent/CN102701315A/en
Application granted granted Critical
Publication of CN102701315B publication Critical patent/CN102701315B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Catalysts (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)

Abstract

The invention discloses a method for processing dye wastewater by applying nanocomposite photocatalyst combination-Fenton, relating a method for processing the dye wastewater. The method comprises the following steps of: pre-processing the surface of a Ti plate; preparing a solution containing fluoride ions; oxidizing an anode to obtain a Ti-based TiO2 nanotube array photocatalyst on the surface of the Ti plate, wherein the Ti plate serves as the anode, and a platinum sheet serves as a counter electrode; preparing Fe (NO3)3 aqueous solution; preserving constant temperature in water bath until the solution is turned from slight yellow into red brown; immersing the Ti-based TiO2 nanotube array photocatalyst into the Fe (NO3)3 aqueous solution for ultrasound; drying and heating to obtain a Ti-based Fe2O3/TiO2 nanotube array composite photocatalyst; placing in a reactor loaded with the dye wastewater; adding H2O2; regulating pH of the solution to be between 2 and 10; taking a spherical mercury lamp as a light source; performing photocatalysis to degrade the dye wastewater in the condition of oxygen; and taking out the Ti-based Fe2O3/TiO2 nanotube array composite photocatalyst and cleaning.

Description

The method of nano composite photo-catalyst coupling class-Fenton dye wastewater treatment using
Technical field
The present invention relates to a kind of treatment process of waste water from dyestuff, especially relate to the method for a kind of nano composite photo-catalyst coupling class-Fenton dye wastewater treatment using.
Background technology
In high-level oxidation technology, like O 3, O 3/ H 2O 2, Fenton (Fenton), UV, UV/O 3, UV/H 2O 2, O 3/ UV/H 2O 2, the Fenton method has advantages such as speed of response is fast, simple and easy to operate, because Fenton reagent has extremely strong oxidation capacity, is specially adapted to the degraded and the mineralising of the organic pollutant that bio-refractory or general chemical oxidation be difficult to take effect.Usually the Fenton method is the homogeneous catalysis oxidation style, with H 2O 2Be oxygenant, Fe 2+Or Fe 3+Be catalyzer, Fe in water 2+Or Fe 3+With H 2O 2Effect produces the hydroxyl radical free radical of strong oxidation, can cause Kettenreaktion at normal temperatures, and the organism of difficult degradation in the waste water from dyestuff finally is oxidized to CO 2, H 2O and other small molecules inorganics.Yet the ferrous ion in the Fenton reagent is dissolved in that facile hydrolysis becomes ferrous hydroxide in the water, thereby loses katalysis, has reduced the transformation efficiency of hydrogen peroxide to hydroxyl radical free radical, causes oxidation capacity to reduce, and the hydrogen peroxide utilization ratio is low.Therefore, handling certain density waste water from dyestuff needs a large amount of reagent dosages, causes increase (1.I.K.Konstantinou, T.A.Albanis, the TiO of dye wastewater treatment cost 2-assisted photocatalytic degradation of azo dyes in aqueous solution:kinetic and mechanistic investigations A review.Appl.Catal., B:Environ.49 (2004) 1-14).
Photochemical catalysis is a kind of heterogeneous oxidation technology, and it is the oxidising process under semi-conductor exists.TiO 2Be a kind of maximum photocatalyst of studying and use, particularly utilize the TiO of anonizing in the preparation of Ti metal substrate surface 2Nano-tube array has particular structural and characteristic, is superior to powder TiO having demonstrated some aspect the photocatalytic degradation pollutent 2The performance of photocatalyst (2.J.M.Macak, M.Zlamal, J.Krysa, P.Schmuki, Self-organized TiO 2Nanotube layers as highly efficient photocatalysts.Small, 2007,3,300; 3.H.F.Zhuang; C.J.Lin; Y.K.Lai, L.Sun, J.Li.Some critical structure factors of titanium oxide nanotube array in its photocatalytic activity.Environ.Sci.& Technol.; 2007,41:4735-4740).Yet, TiO 2The light induced electron of nano-tube array and the recombination rate in hole are still higher, and photocatalytic activity is low, have limited its practical application in photocatalysis field.To TiO 2Nano-tube array is modified, modification becomes one of focal issue of research.The material that Fe is a kind of cheapness, be easy to get, existing research shows, at TiO 2A spot of Fe mixes in the nano-tube array 3+Perhaps use Fe 2O 3Nano particle carries out sensitization to it can prolong the right life-span of light induced electron-hole, improves TiO 2Quantum yield (4.L.Sun, J.Li, C.L.Wang, S.F.Li, C.J.Lin.An electrochemical strategy of doping Fe 3+Into TiO 2Nanotube array films for enhancement in UV photocatalytic activity.Sol.Energy Mater.& Sol.Cells, 2009,93:1875-1880; 5.A.I.Kontos, V.Likodimos, T.Stergiopoulos, D.S.Tsoukleris, P.Falaras, I.Rabias, G.Papavassiliou, D.Kim, J.Kunze, P.Schmuki, Self-organized anodic TiO 2Nanotube arrays functionalized by iron oxide nanoparticles, Chem.Mater.21 (2009) 662-672).But these methods are to TiO 2The effect that the nano-tube array photocatalytic activity improves is still very limited.
It is to improve one of the efficiency of light energy utilization of photocatalyst and most effectual way of speed of reaction at present that high-level oxidation technology is combined with photocatalysis technology.In order to address the above problem, with Fe 3+Mix or Fe 2O 3The TiO of sensitization 2The photochemical catalysis of nano-tube array organically combines with the Fenton oxidation, can reach efficiently, the purpose of decomposing organic pollutant apace.
Summary of the invention
The object of the present invention is to provide the method for a kind of nano composite photo-catalyst coupling class-Fenton dye wastewater treatment using.
Technical scheme of the present invention is with Ti base Fe 2O 3/ TiO 2Nano-tube array is a photocatalyst, in the light-catalyzed reaction system, and Fe 2O 3Lysate (Fe in acidic solution 3+) with the H that adds 2O 2Constitute class-Fenton system, utilize Fe 2O 3/ TiO 2The organic pollutant of difficult degradation in the photocatalysis of nano-tube array and decomposition of the strong oxidation of class-Fenton and the mineralized water.
The present invention includes following steps:
1) with the surface preparation of Ti plate, preparation contains the solution of fluorion, is anode with the Ti plate, and platinized platinum is a counter electrode, after the anodic oxidation, obtains unformed TiO structurally ordered, controllable size on Ti plate surface 2Nano-tube array photocatalyst, i.e. Ti base TiO 2The nano-tube array photocatalyst;
2) preparation Fe (NO 3) 3The aqueous solution, constant temperature to solution becomes reddish-brown by little xanthochromia in the water-bath, with the Ti base TiO for preparing in the step 1) 2The nano-tube array photocatalyst immerses Fe (NO 3) 3Ultrasonic in the aqueous solution, dry post-heat-treated obtains Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst;
3) with step 2) Ti that obtains base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into the reactor drum that waste water from dyestuff is housed, to wherein adding H 2O 2, the pH of regulator solution is 2～10, is light source with the spherical mercury lamp, under logical oxygen condition, carries out photocatalytic degradation of dye waste water;
4) with Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst takes out, and reuses after the water ultrasonic cleaning.
In step 1), said the surface preparation of Ti plate can be mechanical grinding to no marking and ultrasonic cleaning is clean with Ti plate surface; Said anodised condition can be: anodic oxidation 0.5～10h under the voltage of 10～50V.
In step 2) in, said Fe (NO 3) 3The concentration of the aqueous solution can be 0.01～0.1mmolL -1The temperature of said water-bath can be 50 ℃; The said ultransonic time can be 3～120min; Said heat treated condition can be 500 ℃ of thermal treatment 2h in retort furnace.
In step 3), the add-on of said waste water from dyestuff can be 200mL, and the concentration of said waste water from dyestuff can be 0～200mgL -1Said adding H 2O 2Concentration can be 0.1～4.0mmolL -1
The principle that the present invention adopts is: on the one hand, under UV-irradiation, TiO 2Electronics on the valence band is excited, and produces hole and electronics, the redox degradation of dye waste water; On the other hand, TiO 2The Fe of nano-tube array surface attachment 2O 3Dissolving under acidic conditions generates Fe 3+With the H that adds 2O 2Constitute class-Fenton system, finally Synergistic degradation waste water from dyestuff effectively.Its reaction process is following:
Fe 2O 3+H +→Fe 3++H 2O (2)
Fe 3++e -→Fe 2+ (3)
H 2O 2+e -→·OH+OH - (4)
Figure BDA00001820040900032
H 2O 2+Fe 2+→Fe 3++·OH+OH - (6)
H 2O 2+e -→·OH+OH - (7)
RH (organism)+OH → H 2O+R (midbody) → further is oxidized to degradable product (8)
Owing to adopt technique scheme, so the present invention has following beneficial effect:
(1) the present invention is with Ti base Fe 2O 3/ TiO 2The photocatalysis of nanotube array composite photochemical catalyst and H 2O 2The advanced oxidation effect of reagent combines, and has improved Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is to the photocatalysis treatment efficient of waste water from dyestuff.
(2) the present invention has overcome the deficiency that single method exists in dye wastewater treatment using, has reduced H 2O 2Reagent dosage has reduced the processing cost of waste water from dyestuff, has improved the efficient of photocatalysis treatment waste water from dyestuff.
(3) base of the Ti among the present invention Fe 2O 3/ TiO 2The nanotube array composite photochemical catalyst good stability has environmental protection, efficient, reusable characteristics.
Description of drawings
Fig. 1 is for being 50mg L in pH=6.5,200mL concentration -1Dye solution in various assembly catalyze modes to the degradation rate of dyestuff.In Fig. 1, X-coordinate is the dye solution combination, and ordinate zou is degradation rate Removal Rate (%); Ti base Fe wherein 2O 3/ TiO 2Nanotube array composite photochemical catalyst all is that ultrasonic 25min is obtained, the H of adding 2O 2Amount of reagent is 0.375mmol.
Embodiment
Embodiment 1
(1) base material is thick 2mm, is of a size of the industrial Ti plate of 2cm * 3cm, polished to no marking with abrasive paper for metallograph in its surface, and clean with acetone, ethanol and three water ultrasonic cleaning, dry for use.The electrolytic solution of preparation 0.5wt% HF is anode with industrial Ti plate at room temperature, is counter electrode with platinum, electrochemical anodic oxidation 1h under 30V voltage, and thermal treatment 2h under 500 ° of C promptly obtains orderly TiO on industrial Ti plate surface again 2Nano-tube array photocatalyst, i.e. Ti base TiO 2The nano-tube array photocatalyst.
(2) Ti base TiO 2Nano-tube array photocatalyst for degrading waste water from dyestuff.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, and regulation system pH value is 6.5, puts into titanium base TiO again 2The nano-tube array photocatalyst.Reaction is initially at bubbling air under the dark attitude, stirs 30min, reaches the adsorption desorption balance, is that light source carries out illumination with 200W ultra-high voltage spherical mercury lamp then, and every separated 30min extracts water sample, measures the variation of system absorbancy, obtains the degradation rate of waste water from dyestuff.
Fig. 1 is given in pH=6.5,200mL concentration is 50mg L -1Dye solution in various assembly catalyze modes to the degradation rate of dyestuff, Ti base Fe wherein 2O 3/ TiO 2Nanotube array composite photochemical catalyst all is that ultrasonic 25min is obtained, the H of adding 2O 2Amount of reagent is 0.375mmol.
Embodiment 2
H 2O 2Degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, and regulating the pH value is 6.5, adds 0.125mmol H 2O 2, degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp whenever extracts water sample at a distance from 30min then, measures the variation of waste water from dyestuff absorbancy, obtains the degradation rate of waste water from dyestuff.
Embodiment 3
H 2O 2Degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, and regulating the pH value is 6.5, adds 0.375mmol H 2O 2, degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp whenever extracts water sample at a distance from 30min then, measures the variation of waste water from dyestuff absorbancy, obtains the degradation rate of waste water from dyestuff.
Embodiment 4
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Ti base TiO 2The nano-tube array photocatalyst is worked in coordination with H 2O 2The reagent degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, and regulating the pH value is 6.5, with Ti base TiO 2The nano-tube array photocatalyst is put into waste water from dyestuff, adds 0.375mmol H 2O 2Reaction is initially under the dark attitude stirs 30min, reaches adsorption equilibrium, and degradation of dye waste water under the irradiation of 200W ultra-high voltage ball type mercury lamp whenever extracts water sample at a distance from 30min then, measures the variation of waste water from dyestuff absorbancy, obtains the degradation rate of waste water from dyestuff.
Embodiment 5
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Fe (NO of preparation 0.01M 3) 3The aqueous solution, constant temperature 20min becomes reddish-brown by little xanthochromia to solution in 50 ° of C water-baths, with Ti base TiO of preparation in (1) 2The nano-tube array photocatalyst immerses Fe (NO 3) 3Ultrasonic 15min in the aqueous solution takes out back normal temperature seasoning, and is subsequent use behind 500 ° of C calcining 2h in retort furnace then.
(3) Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is worked in coordination with H 2O 2The reagent degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, and regulating the pH value is 6.5, with the Ti base Fe that obtains in (2) 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into waste water from dyestuff, adds 0.375mmol H 2O 2Reaction is initially under the dark attitude stirs 30min, reaches adsorption equilibrium, and degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp whenever extracts water sample at a distance from 30min then, measures the variation of waste water from dyestuff absorbancy, obtains the degradation rate of waste water from dyestuff.
Embodiment 6
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Ti base Fe 2O 3/ TiO 2The preparation of nanotube array composite photochemical catalyst is with embodiment 6.
(3) Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is worked in coordination with H 2O 2The reagent degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, and regulating the pH value is 6.5, with the resulting Ti base of ultrasonic 25min in (2) Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into wherein.Reaction is initially under the dark attitude stirs 30min, reaches adsorption equilibrium, and degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp whenever extracts water sample at a distance from 20min then, measures the variation of system absorbancy, obtains the degradation rate of waste water from dyestuff.
Embodiment 7
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Fe (NO of preparation 0.01M 3) 3Solution, 50 ° of C constant temperature water bath 20min to solution by little xanthochromia reddish-brown, with Ti base TiO of preparation in (1) 2The nano-tube array photocatalyst immerses Fe (NO 3) 3Ultrasonic 25min in the solution takes out back normal temperature seasoning, and is subsequent use behind 500 ° of C calcining 2h in retort furnace then.
(3) Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is worked in coordination with H 2O 2The reagent degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, and regulating the pH value is 6.5, with the resulting Ti base of ultrasonic 25min in (2) Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into wherein, adds 0.125mmol H 2O 2Reaction is initially under the dark attitude stirs 30min, reaches adsorption equilibrium, and degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp whenever extracts water sample at a distance from 30min then, measures the variation of waste water from dyestuff absorbancy, obtains the degradation rate of waste water from dyestuff.
Embodiment 8
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Fe (NO of preparation 0.01M 3) 3Solution, 50 ° of C constant temperature water bath 20min to solution by little xanthochromia reddish-brown, with Ti base TiO of preparation in (1) 2The nano-tube array photocatalyst immerses Fe (NO 3) 3Ultrasonic 25min in the solution takes out back normal temperature seasoning, and is subsequent use behind 500 ° of C calcining 2h in retort furnace then.
(3) Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is worked in coordination with H 2O 2The reagent degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, and regulating the pH value is 6.5, with the resulting Ti base of ultrasonic 25min in (2) Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into wherein, adds 0.375mmol H 2O 2Reaction is initially under the dark attitude stirs 30min, reaches adsorption equilibrium, and degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp whenever extracts water sample at a distance from 30min then, measures the variation of waste water from dyestuff absorbancy, obtains the degradation rate of waste water from dyestuff.
Embodiment 9
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Ti base Fe 2O 3/ TiO 2The preparation of nanotube array composite photochemical catalyst is with embodiment 6.
(3) Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is worked in coordination with H 2O 2The reagent degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, and regulating the pH value is 6.5, adds 3.75mmol H 2O 2, with the resulting Ti base of ultrasonic 25min in (2) Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into wherein.Reaction is initially under the dark attitude stirs 30min, reaches adsorption equilibrium, and degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp whenever extracts water sample at a distance from 20min then, measures the variation of system absorbancy, obtains the degradation rate of waste water from dyestuff.
Embodiment 10
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Fe (NO of preparation 0.01M 3) 3Solution, 50 ° of C constant temperature water bath 20min to solution by little xanthochromia reddish-brown, with Ti base TiO of preparation in (1) 2The nano-tube array photocatalyst immerses Fe (NO 3) 3Ultrasonic 90min in the solution takes out back normal temperature seasoning, and is subsequent use behind 500 ° of C calcining 2h in retort furnace then.
(3) Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is worked in coordination with H 2O 2The reagent degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, and regulating the pH value is 6.5, with the resulting Ti base of ultrasonic 90min in (2) Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into wherein, adds 0.375mmol H 2O 2Reaction is initially under the dark attitude stirs 30min, reaches adsorption equilibrium, and degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp whenever extracts water sample at a distance from 30min then, measures the variation of waste water from dyestuff absorbancy, obtains the degradation rate of waste water from dyestuff.
Embodiment 11
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Ti base Fe 2O 3/ TiO 2The preparation of nanotube array composite photochemical catalyst is with embodiment 6.
(3) Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is worked in coordination with H 2O 2The reagent degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, adds 0.375mmol H 2O 2, regulating the pH value is 10, and ultrasonic 25min in (2) is obtained Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into wherein; Reaction is initially under the dark attitude stirs 30min; Reach adsorption equilibrium, degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp is every at a distance from 30min extraction water sample then; Measure the variation of waste water from dyestuff absorbancy, obtain the degradation rate of waste water from dyestuff.
Embodiment 12
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Ti base Fe 2O 3/ TiO 2The preparation of nanotube array composite photochemical catalyst is with embodiment 6.
(3) Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is worked in coordination with H 2O 2The reagent degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, adds 0.375mmol H 2O 2, regulating the pH value is 3, and ultrasonic 25min in (2) is obtained Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into wherein; Reaction is initially under the dark attitude stirs 30min; Reach adsorption equilibrium, degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp is every at a distance from 30min extraction water sample then; Measure the variation of waste water from dyestuff absorbancy, obtain the degradation rate of waste water from dyestuff.
Embodiment 13
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Ti base Fe 2O 3/ TiO 2The preparation of nanotube array composite photochemical catalyst is with embodiment 6.
(3) Ti base Fe 2O 3/ TiO 2The nanotube array composite photochemical catalyst degradation of dye waste water.With 200mL, 50mg L -1Waste water from dyestuff places reactor drum, and regulating pH value is 3, the basic Fe of Ti that ultrasonic 25min in (2) is obtained 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into wherein; Reaction is initially under the dark attitude stirs 30min; Reach adsorption equilibrium, degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp is every at a distance from 30min extraction water sample then; Measure the variation of waste water from dyestuff absorbancy, obtain the degradation rate of waste water from dyestuff.
Embodiment 14
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Ti base Fe 2O 3/ TiO 2The preparation of nanotube array composite photochemical catalyst is with embodiment 6.
(3) Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is worked in coordination with H 2O 2The reagent degradation of dye waste water.With 200mL, 10mg L -1Waste water from dyestuff places reactor drum, adds 0.375mmol H 2O 2, regulating the pH value is 3, and ultrasonic 25min in (2) is obtained Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into wherein; Reaction is initially under the dark attitude stirs 30min; Reach adsorption equilibrium, degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp is every at a distance from 30min extraction water sample then; Measure the variation of waste water from dyestuff absorbancy, obtain the degradation rate of waste water from dyestuff.
Embodiment 15
(1) Ti base TiO 2The preparation of nano-tube array photocatalyst is with embodiment 1.
(2) Ti base Fe 2O 3/ TiO 2The preparation of nanotube array composite photochemical catalyst is with embodiment 6.
(3) Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is worked in coordination with H 2O 2The reagent degradation of dye waste water.With 200mL, 150mg L -1Waste water from dyestuff places reactor drum, adds 0.375mmol H 2O 2, regulating the pH value is 3, and ultrasonic 25min in (2) is obtained Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into wherein; Reaction is initially under the dark attitude stirs 30min; Reach adsorption equilibrium, degradation of dye waste water under the irradiation of 200W ultra-high voltage spherical mercury lamp is every at a distance from 30min extraction water sample then; Measure the variation of waste water from dyestuff absorbancy, obtain the degradation rate of waste water from dyestuff.
Each embodiment parameter and degradation rate are referring to table 1.
Table 1 embodiment parameter and degradation rate
Figure BDA00001820040900081
Method characteristics involved in the present invention are: make full use of Ti base Fe 2O 3/ TiO 2The photocatalysis of nanotube array composite photochemical catalyst and Fe 2O 3Be dissolved in the Fe in the acidic solution 3+With add H 2O 2Organic pollutant in the oxygenizement Synergistic degradation waste water from dyestuff of reagent formation class-Fenton system has overcome the deficiency that single method exists in degradation of dye waste water, reduced H 2O 2Reagent dosage has reduced the processing cost of waste water from dyestuff, has improved the photocatalysis treatment efficient of waste water from dyestuff, has very high practical value, is a kind of environmental protection, dye wastewater treatment technology efficiently.

Claims (9)

1. the method for nano composite photo-catalyst coupling class-Fenton dye wastewater treatment using is characterized in that may further comprise the steps:
1) with the surface preparation of Ti plate, preparation contains the solution of fluorion, is anode with the Ti plate, and platinized platinum is a counter electrode, after the anodic oxidation, obtains unformed TiO structurally ordered, controllable size on Ti plate surface 2Nano-tube array photocatalyst, i.e. Ti base TiO 2The nano-tube array photocatalyst;
2) preparation Fe (NO 3) 3The aqueous solution, constant temperature to solution becomes reddish-brown by little xanthochromia in the water-bath, with the Ti base TiO for preparing in the step 1) 2The nano-tube array photocatalyst immerses Fe (NO 3) 3Ultrasonic in the aqueous solution, dry post-heat-treated obtains Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst;
3) with step 2) Ti that obtains base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst is put into the reactor drum that waste water from dyestuff is housed, to wherein adding H 2O 2, the pH of regulator solution is 2～10, is light source with the spherical mercury lamp, under logical oxygen condition, carries out photocatalytic degradation of dye waste water;
4) with Ti base Fe 2O 3/ TiO 2Nanotube array composite photochemical catalyst takes out, and reuses after the water ultrasonic cleaning.
2. the method for nano composite photo-catalyst coupling class as claimed in claim 1-Fenton dye wastewater treatment using is characterized in that in step 1), and said is that Ti plate surface is mechanical grinding to no marking and ultrasonic cleaning is clean with the surface preparation of Ti plate.
3. the method for nano composite photo-catalyst coupling class as claimed in claim 1-Fenton dye wastewater treatment using is characterized in that in step 1), and said anodised condition is: anodic oxidation 0.5～10h under the voltage of 10～50V.
4. the method for nano composite photo-catalyst coupling class as claimed in claim 1-Fenton dye wastewater treatment using is characterized in that in step 2) in, said Fe (NO 3) 3The concentration of the aqueous solution is 0.01～0.1mmolL -1
5. the method for nano composite photo-catalyst coupling class as claimed in claim 1-Fenton dye wastewater treatment using is characterized in that in step 2) in, the temperature of said water-bath is 50 ℃.
6. the method for nano composite photo-catalyst coupling class as claimed in claim 1-Fenton dye wastewater treatment using is characterized in that in step 2) in, the said ultransonic time is 3～120min.
7. the method for nano composite photo-catalyst coupling class as claimed in claim 1-Fenton dye wastewater treatment using is characterized in that in step 2) in, said heat treated condition is 500 ℃ of thermal treatment 2h in retort furnace.
8. the method for nano composite photo-catalyst coupling class as claimed in claim 1-Fenton dye wastewater treatment using is characterized in that in step 3) the add-on of said waste water from dyestuff is 200mL, and the concentration of said waste water from dyestuff is 0～200mgL -1
9. the method for nano composite photo-catalyst coupling class as claimed in claim 1-Fenton dye wastewater treatment using is characterized in that in step 3), said adding H 2O 2Concentration be 0.1～4.0mmolL -1
CN201210218653.8A 2012-06-28 2012-06-28 Method for processing dye wastewater by applying nanocomposite photocatalyst combination-Fenton Active CN102701315B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201210218653.8A CN102701315B (en) 2012-06-28 2012-06-28 Method for processing dye wastewater by applying nanocomposite photocatalyst combination-Fenton

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201210218653.8A CN102701315B (en) 2012-06-28 2012-06-28 Method for processing dye wastewater by applying nanocomposite photocatalyst combination-Fenton

Publications (2)

Publication Number Publication Date
CN102701315A true CN102701315A (en) 2012-10-03
CN102701315B CN102701315B (en) 2014-04-09

Family

ID=46894455

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201210218653.8A Active CN102701315B (en) 2012-06-28 2012-06-28 Method for processing dye wastewater by applying nanocomposite photocatalyst combination-Fenton

Country Status (1)

Country Link
CN (1) CN102701315B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103446699A (en) * 2013-09-06 2013-12-18 广西大学 Method for cooperatively degrading organic matters by visible light photoelectric-Fenton
CN104037398A (en) * 2014-03-12 2014-09-10 华中师范大学 TiO2@Fe2O3 layered multistage composite nanometer array material and preparation method and applications thereof
CN105195185A (en) * 2015-09-18 2015-12-30 武汉理工大学 Efficient light fenton catalyst Ag3PO4/CuO and preparation method thereof
CN107754843A (en) * 2017-10-24 2018-03-06 江苏大学 The composite photo-catalysts of Fe2O3 doping HTS Fe TS 1, preparation method and application
CN108404958A (en) * 2018-03-07 2018-08-17 武汉理工大学 Doping titanium dioxide catalyst carrier in situ and its preparation method and application
CN111450854A (en) * 2020-04-21 2020-07-28 东华工程科技股份有限公司 Efficient nano photo-Fenton catalyst and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060079172A (en) * 2006-06-15 2006-07-05 (주)미시간기술 A water and wastewater treatment system and method using advanced oxidation processes(uv with catalyst, fenton, ozone) and pressurized ozone oxidation(aop-po2)
CN101956223A (en) * 2010-10-27 2011-01-26 厦门大学 Method for preparing cuprous oxide composite titanium dioxide nanotube array
CN102008967A (en) * 2010-11-01 2011-04-13 清华大学 Ferric sulfate catalyst and preparation method thereof
CN102424466A (en) * 2011-10-25 2012-04-25 厦门大学 Dye wastewater treatment method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20060079172A (en) * 2006-06-15 2006-07-05 (주)미시간기술 A water and wastewater treatment system and method using advanced oxidation processes(uv with catalyst, fenton, ozone) and pressurized ozone oxidation(aop-po2)
CN101956223A (en) * 2010-10-27 2011-01-26 厦门大学 Method for preparing cuprous oxide composite titanium dioxide nanotube array
CN102008967A (en) * 2010-11-01 2011-04-13 清华大学 Ferric sulfate catalyst and preparation method thereof
CN102424466A (en) * 2011-10-25 2012-04-25 厦门大学 Dye wastewater treatment method

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A. I. KONTOS ET AL: "Self-Organized Anodic TiO2 Nanotube Arrays Functionalized by Iron Oxide Nanoparticles", 《CHEM.MATER》 *
何开棘 等: "掺铁纳米TiO2粉体的制备及其光催化活性的研究", 《鞍山科技大学学报》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103446699A (en) * 2013-09-06 2013-12-18 广西大学 Method for cooperatively degrading organic matters by visible light photoelectric-Fenton
CN104037398A (en) * 2014-03-12 2014-09-10 华中师范大学 TiO2@Fe2O3 layered multistage composite nanometer array material and preparation method and applications thereof
CN105195185A (en) * 2015-09-18 2015-12-30 武汉理工大学 Efficient light fenton catalyst Ag3PO4/CuO and preparation method thereof
CN107754843A (en) * 2017-10-24 2018-03-06 江苏大学 The composite photo-catalysts of Fe2O3 doping HTS Fe TS 1, preparation method and application
CN107754843B (en) * 2017-10-24 2020-06-09 江苏大学 Fe-doped titanium silicalite Fe-TS-1 composite photocatalyst, preparation method and application
CN108404958A (en) * 2018-03-07 2018-08-17 武汉理工大学 Doping titanium dioxide catalyst carrier in situ and its preparation method and application
CN111450854A (en) * 2020-04-21 2020-07-28 东华工程科技股份有限公司 Efficient nano photo-Fenton catalyst and preparation method thereof
CN111450854B (en) * 2020-04-21 2023-02-17 东华工程科技股份有限公司 Efficient nano photo-Fenton catalyst and preparation method thereof

Also Published As

Publication number Publication date
CN102701315B (en) 2014-04-09

Similar Documents

Publication Publication Date Title
CN102701315B (en) Method for processing dye wastewater by applying nanocomposite photocatalyst combination-Fenton
Doudrick et al. Nitrate reduction in water using commercial titanium dioxide photocatalysts (P25, P90, and Hombikat UV100)
Yin et al. Photocatalytic oxidation of NO x under visible LED light irradiation over nitrogen-doped titania particles with iron or platinum loading
Siuleiman et al. Photodegradation of Orange II by ZnO and TiO2 powders and nanowire ZnO and ZnO/TiO2 thin films
Daskalaki et al. Solar light-induced degradation of bisphenol-A with TiO2 immobilized on Ti
Chuaicham et al. Importance of ZnTiO3 phase in ZnTi-mixed metal oxide photocatalysts derived from layered double hydroxide
Wang et al. Photocatalytic degradation of metronidazole in aqueous solution by niobate K6Nb10. 8O30
CN103818986A (en) Photocatalytic electrode responding to visible lights and application thereof on chromium-containing wastewater treatment
Deshpande et al. Controlled nanostructured morphology of BiVO4 photoanodes for efficient on-demand catalysis in solar water-splitting and sustainable water-treatment
CN102424466B (en) Dye wastewater treatment method
Lee et al. Photocatalytic characteristics of boron and nitrogen doped titania film synthesized by micro-arc oxidation
CN104941615A (en) Preparation method of Ag/AgCl/TiO2 nanotube
Wang et al. A modified Z-scheme Er3+: YAlO3@(PdS/BiPO4)/(Au/rGO)/CdS photocatalyst for enhanced solar-light photocatalytic conversion of nitrite
Saadati et al. Combining brown titanium dioxide with BiOBr and AgBr nanoparticles using a facile one-pot procedure to promote visible-light photocatalytic performance
CN106582812A (en) Composite photocatalyst with titanium dioxide axially functionalized by metallic zinc porphyrin and preparation method thereof
Nahyoon et al. Efficient degradation of rhodamine B with sustainable electricity generation in a photocatalytic fuel cell using visible light Ag3PO4/Fe/GTiP photoanode and ZnIn2S4 photocathode
Kozlova et al. Overall water splitting over Pt/TiO2 catalyst with Ce3+/Ce4+ shuttle charge transfer system
Keerthana et al. NiMoO4 nanorods photocatalytic activity comparison under UV and visible light
Hu et al. Hollow Fe3+-doped anatase titanium dioxide nanosphere for photocatalytic degradation of organic dyes
CN104324743A (en) Preparation method of nitrogen-doped TiO2 nanotube composite Fe2O3 catalyst
CN104368338A (en) Preparation method of amino-modified Pd/TiO2 photocatalyst
Sun et al. Enhancement of catalytic degradation of rhodamine b under sunlight with au loading TiO2 nanotube arrays
Raza et al. Photocatalytic dye degradation using modified titania
Pouretedal et al. Photodegradation of para-nitrophenol catalyzed by Fe2O3/FeS nanocomposite
CN107096549A (en) A kind of preparation method of the compound silver bromide photochemical catalyst of wolframic acid silver

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20160406

Address after: 526060 Taining village, Duanzhou industrial city, Guangdong, Zhaoqing

Patentee after: Zhaoqing Huafeng Electronic foil Limited by Share Ltd Bijiang environmental protection branch

Address before: Xiamen City, Fujian Province, 361005 South Siming Road No. 422

Patentee before: Xiamen University

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20171011

Address after: 526060 Guangdong city of Zhaoqing Province Gaoyao district town of clay area (nine Huafeng Electronic aluminum foil Co. Ltd.) fifth plant

Patentee after: Guangdong Huafeng Bijiang Environmental Technology Co. Ltd.

Address before: 526060 Taining village, Duanzhou industrial city, Guangdong, Zhaoqing

Patentee before: Zhaoqing Huafeng Electronic foil Limited by Share Ltd Bijiang environmental protection branch